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一种用于在水中对 Hg(II)和 Cu(II)进行区分检测的三吡啶-罗丹明杂化荧光探针及其在分子逻辑门和细胞成像中的应用。

A terpyridyl-rhodamine hybrid fluorescent probe for discriminative sensing of Hg (II) and Cu (II) in water and applications for molecular logic gate and cell imaging.

机构信息

School of Chemistry and Chemical Engineering, Key Laboratory of Chemical Synthesis and Pollution Control of Sichuan Province, China West Normal University, Nanchong 637002, China.

Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2023 Dec 5;302:123124. doi: 10.1016/j.saa.2023.123124. Epub 2023 Jul 10.

Abstract

Sensitive and discriminative sensing of more than one analyte with a single fluorescent probe is significant and challenging. Herein a new terpyridyl-rhodamine hybrid, namely TRH, has been rationally designed and prepared with two responsive groups in the molecular structure, which facilitate the discriminative detection of Hg and Cu ions in water with detection limits of 4.9 and 53.3 nM by ratiometric fluorescence change (F/F) and fluorescence quenching, respectively. Investigations show that the selectivity to Hg ions can be attributed to Hg-promoted spirolactam ring opening and further hydrolysis, followed by a through-bond energy transfer (TBET) process. The selective fluorescence quenching to Cu ions probably can be ascribed to the binding Cu to terpyridyl that triggers a ligand-to-metal charge transfer (LMCT) process, which can also efficiently inhibit the TBET process induced by Hg ions and promotes the discriminative sensing of Cu (II) and Hg (II). In addition, the fluorescent responses to Hg and Cu ions cover a wide pH range. Moreover, a combinatorial logic gate with the functions of NOR and INHIBIT has been fabricated by using Hg and Cu ions as chemical input signals, and fluorescence at 485 and 595 nm as output signals. Besides, TRH also exhibits sensitive and discriminative sensing ability to Hg and Cu ions by the fluorescence of rhodamine fluorophore. Significantly, based on the fluorescence signal output of rhodamine moiety, TRH can be used as a tracer for the discriminative sensing of Hg and Cu ions by using living cells.

摘要

对单一荧光探针进行多分析物的灵敏和有区别的传感具有重要意义,同时也极具挑战性。在此,我们设计并制备了一种新的三吡啶-罗丹明杂合体,即 TRH,其分子结构中包含两个响应基团,这有利于通过比率荧光变化(F/F)和荧光猝灭分别以检测限为 4.9 和 53.3 nM 对 Hg 和 Cu 离子进行有区别的检测。研究表明,对 Hg 离子的选择性可归因于 Hg 促进螺环内酰胺开环和进一步水解,随后发生通过键的能量转移(TBET)过程。对 Cu 离子的选择性荧光猝灭可能归因于 Cu 与三吡啶的结合引发配体到金属电荷转移(LMCT)过程,这也可以有效地抑制 Hg 离子诱导的 TBET 过程并促进 Cu(II)和 Hg(II)的有区别的传感。此外,对 Hg 和 Cu 离子的荧光响应覆盖很宽的 pH 范围。此外,通过将 Hg 和 Cu 离子用作化学输入信号,并将 485 和 595nm 处的荧光用作输出信号,构建了具有 NOR 和 INHIBIT 功能的组合逻辑门。此外,TRH 还通过罗丹明荧光团表现出对 Hg 和 Cu 离子的灵敏和有区别的传感能力。重要的是,基于罗丹明部分的荧光信号输出,TRH 可以用作通过活细胞对 Hg 和 Cu 离子进行有区别的传感的示踪剂。

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